Chromatographic separation using bis(phenyltolyl) ethers



United States Patent 3,216,179 CHROMATOGRAPHIC SEPARATION USING BIS(PHENYLTOLYL) ETHERS James D. Doedens, 20 Rosemary Court, Midland, Mich; Howard P. Cordts, 5448 Kasemeyer Road, Bay City, Mich; and David F. Wisniewski, 4869 Franklin St.,

Auburn, Mich.

N0 Drawing. Original application Aug. 31, 1959, Ser. No. 836,927. Divided and this application June 3, 1964, Ser. No. 378,480

2 Claims. (Cl. 55-67) This is a division of application Serial No. 836,927, filed August 31, 1959.

This invention concerns chemical compositions which are liquid condensation products of a benzenoid hydrocarbon having up to two alkyl substituents containing from 1 to 2 carbon atoms with 4,4-di(chloromethyl)diphenyl oxide, hereinafter abbreviated as DCMDPO. It also concerns their use in chromatography.

The compounds of this invention are unusually effective as absorbents in chromatography, particularly vapor phase chromatography.

The products of this invention are prepared by a condensation or alkylation in the presence ofa Friedel-Crafts catalysts, e.g., ZnCl FeCl BF etc., involving two moles of benzenoid hydrocarbon per mole of DCMDPO when the dialkyl benzenes are coreactants, 3 moles of benzenoid hydrocarbon per two moles of DCMDPO when benzene is the coreactant and a mixed condensate of 2 and 3 moles of benzenoid hydrocarbon per 1 and 2 moles of DCMDPO when a monoalkylbenzene is the coreactant. For example, bis(a-x-xylyl-ptolyl)ether is produced when 2 molar proportions of xylene are condensed with one mole of DCMDPO, x representing a position on the benzene nucleus, oz,oc'-biS((pta-phenyl-p-tolyloxy)phenyl) )-p-xylene is produced when 3 moles of benzene are condensed with 2 moles of DCMDPO, a mixture of approximately 70 weight percent of bis(u-x-tolyl-p-tolyl)ether and approximately 30 percent 2-methyl-1,4-bis((p-(a-x-tolyl p tolyloxy)benzyl)) benzene is produced when toluene present in excess is condensed with DCMDPO, and a mixture of the analogous ethyl homologs, approximately 70 weight percent bis (a-x-ethylphenyl-p-tolyl)ether and approximately 30 percent 2-ethyl-1,4-bis((p-(a-x-ethylphenyl-p tolyloxy)benzyl)) benzene is produced when ethylbenzene present in excess is condensed with DCMDPO. The ethylbenzene and toluene condensation products have mainly para-substitution with a small amount of ortho-substitution. The xylene condensate has mainly 1,2,4-substitution with a small amount of 1,2,3- and 1,2,6-substitution. The indicated positions are those of the alkyl substituents of the benzenoid hydrocarbon moieties relative to the 4,4'-dimethylene diphenyl oxide moieties, hereinafter referred to as diphenyl oxide moieties.

The reaction is carried out by reacting the benzenoid hydrocarbon, present in stoichiometric excess over the DCMDPO, e.g., more than 2 moles of the former to one of the latter, and suflicient in any event to dissolve all of the DCMDPO at reaction temperature in the presence of a small catalytic amount of a Friedel-Crafts catalyst, generally from a trace up to 2 weight percent, DCMDPO basis. A simple trial suffices to determine the amount of benzenoid hydrocarbon sufficient to dissolve the DCMDPO. A reaction temperature between 45 C. and the boiling point of the benzenoid hydrocarbon, generally between 50 and 150 C. and preferably at the boiling point of the benzenoid hydrocarbon reactant is used. Excess benzenoid hydrocarbon acts as a moderating diluent, also expedites reaction in accordance with Le Chateliers Law and, further, prevents self-condensation of the DCMDPO. The reaction is carried out until hydrogen chloride evolution has stopped. At lower temperatures, as expected, longer reaction times are required.

EXAMPLE 1.REACTION OF DCMDPO WITH XYLENE Charge:

107 g. (0.4 mol) DCMDPO 856 g. (8.07 moles) xylene 4 g. zinc chloride The above reactants were charged to a 2-liter B-necked pot equipped with a mechanically driven agitator and two reflux condensers. Heat was applied gradually to 74 C., at which temperature HCl was evolved vigorously. When the HCl evolution had slowed down, the temperature was increased to 135 C. and was held there for 10 hours. The reaction mixture was then cooled and transferred to a separatory funnel where it was washed twice with water, once with aqueous 5 percent NaHCO solution, and again with water. After the final separation, the mixture was filtered and stripped to C. at 25 mm. Hg to rid it of xylene. The residue was then transferred to another still and stripped of solvent to a pot temperature of 270 C. at 0.7 mm. Hg. A quantity of 127 g. liquid product was recovered for a 79.5 percent yield, DCMDPO basis, identified as bis(a-x-xylyl-p-tolyl) ether by infrared analysis and a molecular weight of 400 (calcd.406).

EXAMPLE 2.-REACTION OF DCMDPO WIIH ETHYLBENZENE Charge:

107 g. (0.4 mole) DCMDPO 862 g. (8.07 moles) ethylbenzene 4 g. zinc chloride EXAMPLE 3.REACTION OF DCMDPO WITH TOLUENE A quantity of DCMDPO (534 g., 2 moles) dissolved in toluene (1732 g., 18.8 moles) containing 20 g. zinc chloride was added to a 3-liter 3-necked round bottomed flask equipped with a mechanical agitator, reflux con denser, and thermometer. It was heated with agitation at reflux of the toluene for 2 hours. During the reaction time, HCl was vented through the reflux condenser and a scrubber. The reaciton mixture was cooled to 25 30 C. with agitation. It was then washed three times with an equal volume of cold water, once with aqueous 5 percent sodium bicarbonate solution, and again with water until the aqueous phase .was neutral. The excess toluene and any water was stripped off at a temperature of 250 C.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,216,179 November 9, 1965 James D. Doedens et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

In the grant, lines 1 to 3, for "James D. Doedens, of Midland, Michigan, Howard P. Cordts, of Bay City, Michigan; and David F. Wisniewski, of Auburn, Michigan," read James D. Doedens, of Midland, Michigan, Howard P. Cordts, of Bay City, Michigan, and David F. Wisniewski, of Auburn, Michigan, assignors to The Dow Chemical Company, of Midland, Michigan, a

corporation of Delaware, lines 12 and 13, for "James D. Doedens, Howard P. Cordts and David F. Wisniewski, their heirs" read The Dow Chemical Company, its successors in the heading to the printed specification, lines 4 to 7, for

"James D. Doedens, 2O Rosemary Court, Midland, Mich.; Howard P. Cordts, 5448 Kasemeyer Road, Bay City, Mich. and David F. Wisniewski, 4869 Franklin St., Auburn, Mich." read James D. Doedens, Midland, Mich., Howard P. Cordts, Bay City, Mich., and David F. Wisniewski, Auburn, Mich., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware Signed and sealed this 20th day of September 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A METHOD FOR SEPARATING MIXED ORGANIC SPECIES WHICH COMPRISES BRINGING THE MIXED ORGANIC SPECIES INTO CONTACT WITH A BED OF INERT PARTICULATE PACKING MATERIAL COATED WITH A CONDENSATION PRODUCT OF 4,4''-DI(CHLOROMETHYL)DIPHENYL OXIDE AND BENZENOID HYDROCARBON HAVING THE FORMULA R1R2R3C6H3, WHEREIN C6H3 REPRESENTS A BENZENE MOIETY AND R1, R2 AND R3 INDIVIDUALLY REPRESENT ONE OF THE GROUP OF HYDROGEN AND ALKYL GROUPS HAVING FROM 1 TO 2 CARBON ATOMS AND AT LEAST ONE OF WHICH IS HYDROGEN, SAID CONDENSATION PRODUCTS HAVING FROM 1 TO 2 DIPHENYL OXIDE MOIETIES AND FROM 2 TO 3 BENZENOID HYDROCARBON MOIETIES PER MOLECULE. 